• Journal of the Korean Vacuum Society
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• v.15 no.5
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• pp.527-533
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• 2006

Spinel $LiNi_xMn_{2-x}O_4$ thin films were synthesized up to x = 0.9 by a sol-gel method employing spin-coating. The Ni-substituted films were found to maintain cubic structure at low x but to exhibit tetragonal structure for $x{\geq}0.6$. Such cubic-tetragonal phase transition indicates that $Ni^{3+}(d7)$ ions with low-spin $(t_{2g}^6,e_g^1)$ state occupy the octahedral sites of the compound, thus being subject to the Jahn-Teller distortion. By x-ray photoelectron spectroscopy both $Ni^{2+}$ and $Ni^{3+}$ ions were detected. Optical properties of the $LiNi_xMn_{2-x}O_4$ films were investigated by spectroscopic ellipsometry (SE) in the visible?ultraviolet range. The measured dielectric function spectra by SE mainly consist of broad absorption structures attributed to charge-transfer (CT) transitions, $O^{2-}(2p){\rightarrow}Mn^{4+}(3d)$ for 1.9 $(t_{2g})$ and $2.8{\sim}3.0$ eV $(e_g)$ structures and $O^{2-}(2p){\rightarrow}Mn^{3+}(3d)$ for 2.3 $(t_{2g})$ and $3.4{\sim}3.6$ eV $(e_g)$ structures. Also, sharp absorption structures were observed at about 1.6, 1.7, and 1.9 eV, interpreted as due to d-d crystal-field transitions within the octahedral $Mn^{3+}$ ion. The strengths of these absorption structures are reduced by the Ni substitution. Rapid reduction of the CT transition strength involving the eg states for x = 0.6 is attributed to the reduced wavefunction overlap between the $e_g$ and the $O^{2-}(2p)$ states due to the tetragonal extension of the lattice constant by the Jahn-Teller effect.